WO2016116605A1

WO2016116605A1 - Corrosion-resistant composition and method for preparing a corrosion-resistant layer on a surface of a substrate using said composition

Info

Publication number: WO2016116605A1
Application number: PCT/EP2016/051350
Authority: WO
Inventors: Sébastien CATEL; Sébastien GENTY; Grégoire Herve
Original assignee: Socomore
Priority date: 2015-01-22
Filing date: 2016-01-22
Publication date: 2016-07-28
Also published as: FR3031981B1; ES2935065T3; FR3031981A1; EP3247751A1; EP3247751B1

Abstract

The invention relates to a corrosion-resistant composition comprising at least one organic bonding resin; at least one organic corrosion inhibitor chosen from among compounds comprising at least one thiol function and/or at least one thione function; optionally a solvent; and at least one solid inorganic corrosion inhibitor. The present invention also relates to a method for preparing a corrosion-resistant layer on a surface of a substrate using said composition; a corrosion-resistant layer prepared by said method, and a substrate coated by said layer. The use of said corrosion-resistant layer imparts corrosion-resistance properties to the surface of a substrate.

Description

ANTI-CORROSION COMPOSITION AND METHOD FOR PREPARING ANTI-CORROSION LAYER ON A SURFACE OF A SUBSTRATE USING THE SAME

DESCRIPTION

TECHNICAL AREA

The invention relates to an anti-corrosion composition for preparing an anti-corrosion layer or film, also called a corrosion protection layer or film, on a surface of a substrate, in particular on a surface of a substrate. comprising, a metal and / or an alloy of a metal, and / or a composite material, preferably on a surface of a substrate consisting of a metal and / or an alloy of a metal, and / or a composite material .

Preferably, the metal is aluminum, the alloy is an aluminum alloy and the composite is a thermoplastic polymer (a "plastic") with fiber reinforcements, such as carbon fibers.

The substrate on which the layer is prepared may be bare or already coated, in particular with a paint.

The invention also relates to a method for preparing an anticorrosive layer or film on a surface of a substrate that implements said composition.

The technical field of the invention can be defined, in general, as that of the surface treatment, in particular of surfaces made of metals or alloys of metals or composite materials.

The technical field of the invention can be defined in particular as that of the coating of surfaces of metals, such as aluminum, iron, or titanium, or alloys of metals such as steel or aluminum alloys, or composite materials, which are used for example in the aviation, aerospace, rail, and automobile industries, shipbuilding, oil and gas transportation, wind or water exploration, particularly gas or oil, for example to manufacture motor vehicles (cars, trucks, motorcycles etc.), boats, aircraft (airplanes, helicopters, seaplanes, drones etc.), gas pipelines, pipelines, aqueducts, and offshore platforms.

More specifically, the invention belongs to the technical field of compositions used to coat the surface of optionally painted substrates and to protect the surface of these substrates against aggressive environments such as corrosive atmospheres, and chemical and / or mechanical aggression.

These compositions are generally applied to painted surfaces to protect the underlying structures from possible corrosion in case of defects in the paint layers and even to ensure a long service life of these layers of paint, that is to say that these layers of paint are durable and permanent. This avoids these layers are replaced during the service life of an aircraft for example.

The coatings obtained with these compositions also protect the paint from external attacks, for example condensation, particularly related to the number of passengers, toilet liquids from aircraft, and de-icing products or hydraulic fluids.

STATE OF THE PRIOR ART

Anti-corrosion compositions currently known in the aviation market are such products available from Chemetall ^® under the name ARDROX ^® as ARDROX ^® AV 15, the ARDROX ^® AV 30, or ARDROX ^® AV 35D, or product available from SOCOMORE under the name of SOCOPAC 65 H or the product available from Zip-Chem Products under the name Cor-Ban ^® such as Cor-Ban ^® 35, Cor-Ban ^® 23.

The known compositions are compositions known as "1-K" or single-component compositions, which generally comprise a binder resin and anticorrosion agents in a generally organic solvent.

Although the known compositions make it possible to prepare coatings which have a certain resistance to corrosion, there is still a need for anti-corrosion composition which make it possible to prepare coatings having excellent anti-corrosion properties, and improved with respect to the anticorrosion properties of the coatings obtained with the known anti-corrosion compositions.

The anti-corrosion properties are generally appreciated by means of the Salt Fog Corrosion Resistance (BS) test.

Thus compositions currently commonly used in the field of aeronautics as SOCOPAC 65 ^® H, or ARDROX ^® AV15 when applied to a thickness of 15 μιη (dry film thickness), it possible to obtain a resistor salt spray (BS) 1500 hours for SOCOPAC ^® 65 H or ARDROX AV15 ^® .

The latest composition, the ARDROX ^® AV35D, provides

3000 hours at the SB at 35 μιη sec but this is a two-layer system. In addition, this product is characterized by a drying time of the order of 60-90 minutes, and which strongly depends on the conditions in which the drying is carried out, namely essentially the temperature and humidity. Finally, the low viscosity of this composition can cause coating defects, such as run-off problems when the composition is applied with thicknesses greater than 60 μιη in the wet state.

In addition, the coating obtained with this composition has a very low mechanical strength because it is little or not crosslinked.

This poses problems when the personnel responsible for applying this composition must access a second time to the area where the composition has been applied, because the coating is then trampled and sticks under the feet.

This phenomenon is accentuated in humid and hot environments.

There is also a need for such an anti-corrosion composition which while giving coatings having excellent anti-corrosion properties, advantageously improved over prior art compositions, also has excellent adhesion properties on all kinds of substrates, such as bare and painted aluminum alloys, steels, and bare and painted composites, excellent properties of mechanical resistance and resistance to chemical attack eg solvents, hydraulic fluids and other fluids, such as fluids used in aircraft. The person skilled in the art is constantly seeking to improve the anticorrosive properties but also the mechanical properties of the coatings obtained by using these anti-corrosion compositions in particular since the composition once applied can be trodden by the operators during maintenance or manufacturing operations. .

Such a composition must advantageously have a fast drying time to reduce the durations of the production cycles during manufacture, or during maintenance operations (MRO) and thus reduce the costs associated with these operations. For example, it is sought to have downtimes for shorter ground aircraft.

Such a composition must, moreover, advantageously contain only little or no organic solvents.

The object of the present invention is to provide an anti-corrosion composition that meets the needs and requirements listed above, among others.

The object of the present invention is still to provide an anti-corrosion composition which does not have the limitations, defects and disadvantages of the anticorrosion compositions of the prior art and which provides a solution to the problems of the anti-corrosion compositions of the prior art. .

STATEMENT OF THE INVENTION

This and other objects are achieved, according to the invention, by an anti-corrosion composition characterized in that it comprises:

a) at least one organic binder resin;

b) at least one organic corrosion inhibiting agent selected from compounds comprising at least one thiol function and / or at least one thione function;

c) optionally a solvent; and

d) at least one solid inorganic corrosion inhibiting agent.

The solvent (the solvent is chosen from water, organic solvents and mixtures thereof, preferentially water) is only optional and is added only if it is necessary to adjust the viscosity. Compounds comprising at least one thiol function and / or at least one thione function will also be referred to as convenience mercaptans, mercaptan compounds, or compounds of the family of mercaptans in the following.

The composition according to the invention is a composition called "1-K" or one-component composition or formulation. In other words, the components that make up the composition according to the invention are not stored separately and mixed only shortly before use.

On the contrary, the composition according to the invention once prepared can be stored for a long time, if, however, of course it is not subjected to conditions leading to its drying.

The composition according to the invention has never been described in the prior art.

In particular, the composition according to the invention comprises a specific combination of corrosion inhibiting agents, namely the combination of at least one specific organic corrosion inhibiting agent chosen from compounds comprising at least one thiol function and / or at least one a thione function and at least one solid inorganic corrosion inhibiting agent.

Such a specific combination of corrosion inhibiting agents has never been described in the prior art related to the field of anticorrosive coatings.

Surprisingly, the composition according to the invention makes it possible to prepare layers on substrates, in particular metallic substrates, which, while having excellent anti-corrosion properties, improved with respect to the layers obtained with the compositions of the prior art, generally also exhibit excellent properties of strength, adhesion and resistance to chemical attack.

By way of example, depending on the thickness of the anti-corrosion layer according to the invention, it is possible to obtain salt spray protection levels (BS) of a few hundred hours to several thousand hours in tests performed according to ASTM B117 or ISO 9227: 2012.

This excellent level of protection is obtained with a film whose dry thickness generally ranges from 5 to 50 μιη. By way of example, the adhesion of the anti-corrosion layer according to the invention to the surface, for example made of metal, alloy or composite, is preserved after continuous exposure to moisture. The anti-corrosion layer according to the invention does not exhibit blisters, cracks or delamination even beyond several hundred or even several thousand hours of exposure in a condensation chamber (ISO 6270-1: 1998 / ASTM D4585). Similarly, the film shows no blistering, cracking or delamination after several tens of hours or hundreds of hours spent in a climatic chamber whose temperature and humidity periodically vary, namely respectively -55 ° C to 80 ° C and from 50% RH to 100% RH.

The use in the compositions of the invention of a specific organic corrosion inhibiting agent chosen from compounds comprising at least one thiol function and / or at least one thione function in place of the corrosion inhibitors usually used in the compositions anti-corrosion already leads to an improvement of the anti-corrosion properties and this improvement is further increased when this specific organic corrosion inhibiting agent of the family of mercaptans is combined with a solid inorganic corrosion inhibiting agent.

It should be noted that the composition solves the problem underlying the invention as soon as the essential components a), b) and d) in their most general definition are present. The other components are only optional components that can, however, provide some advantageous properties.

In the same way, the selection of particular components among the components falling within the definition of the essential components a), b) and d), may also provide some advantageous properties.

Advantageously, the composition according to the invention comprises, in% by weight relative to the total weight of the composition:

from 30% to 60% by weight of the organic binder resin;

from 5% to 20% by weight of the organic corrosion inhibiting agent chosen from compounds comprising at least one thiol function and / or at least one thione function;

from 5% to 20% by weight of the solid inorganic corrosion inhibiting agent; from 0% to 50%, preferably from 10% to 40% by weight of the solvent.

It is clear that the sum of the% by weight of the constituents of the composition according to the invention is always 100% by weight.

The composition according to the invention generally has a solids content of 30% to 60% by weight. For higher or lower concentrations, application problems may be observed.

There is no limitation as to the choice of the binder resin of the composition according to the invention.

This binder resin may be chosen from the binder resins commonly used in anti-corrosion compositions.

Advantageously, the binder resin may be chosen from alkyd resins, modified alkyd resins such as modified urethane alkyd resins or epoxy-modified alkyd resins, terpene resins, acrylic resins such as styrene-acrylic resins, hydrocarbon resins, and the like. vinyl resins such as vinyl acrylic resins and vinyl styrenic resins.

Advantageously, the binder resin is chosen from urethane modified alkyd resins also known as urethane alkyd resins.

These modified alkyd resins and in particular modified urethane alkyd resins or acrylic vinyl resins may be available in an organic solvent medium (solvent medium) such as white spirit, or in an aqueous medium, generally in the form of dispersions or emulsions in water. 'water.

Examples of such resins are given in Table I below: Manufacturer's Brand Name Type

Middle

resin resin resin

alkyd

Worlée

aqueous modified Worleesol E 150 W

Chemie

urethane

alkyd

Worlée

Aqueous modified Worleesol E 380W

Chemie

urethane

alkyd

Worlée

aqueous modified Worleesol E 330 W

Chemie

urethane

Vinyl

aqueous Haloflex 202 or 299 DSM

acrylic

Table I.

Resins, and especially modified urethane alkyd resins, in an aqueous medium, which are generally in the form of dispersion or emulsion of these resins in water are still preferred because they give the layers having the best properties.

Indeed, it has been demonstrated that one of the main problems of known anti-corrosion compositions, currently available on the market, is due to the binders, ie the resins used in these compositions.

Indeed, these compositions of the prior art all contain tackifying resins, "tackifying", hydrocarbon resins, or even terpene resins which are resins used in the adhesive field and which have a sufficiently high glass transition temperature Tg. to give the product once formulated an adequate physical drying.

By "physical" drying is meant drying without crosslinking, by simple evaporation of the volatile solvent.

This technology using such resins with a "physical" drying, gives coatings having no dense network, and therefore by definition, no cross-linking at heart. These coatings therefore have very low mechanical strengths and are sensitive to environmental effects, for example atmospheres rich in solvents, high temperatures, condensation, and mechanical stress.

The preferred implementation, according to the invention, of modified alkyd resins leads to crosslinked films with strongly reinforced properties.

These films can also optionally be removed using solvents such as DIESTONE DLS ^® , SOCOCLEAN AQUAFORTE ^® and others that are qualified in the aeronautical field for this type of operation.

This is particularly the case for films prepared from compositions containing the first three resins mentioned in Table I.

The drying times in confined environments, rich in solvent vapors, obtained with the anti-corrosion compositions, according to the invention, containing modified alkyd resins are significantly lower than the drying times obtained with a composition of the prior art, with ARDROX ^® AV 35D, as is clear from Table II below.

Table II: Surface drying of coatings (dry thickness of 35 μιη at room temperature in a chamber of dimensions 220 mm × 100 mm × 100 mm having an opening on the upper part of dimensions 40 mm × 20 mm.

It is found that in these conditions rich in solvents, the composition of the prior art dries very hardly, if ever, because of the non-binding nature of the resins employed, while the drying time of the compositions according to the invention is comparatively very small. The shortest drying times are obtained with the composition according to the invention containing an aqueous dispersion of alkyd resin modified urethane.

An additional advantage related to the preferred implementation of modified alkyd resins in the compositions according to the invention is based on the fact that the drying time can be modulated very easily by the adjustment of siccatives possibly present in the formula, which is technically impossible with the compositions of the prior art not containing such resins, because of the chemical nature of the resins contained in the compositions of the prior art, namely non-crosslinkable resins, which dry "physically" without crosslinking.

In addition, the salt spray resistance (BS) of coatings prepared with the anti-corrosion compositions according to the invention containing modified alkyd resins is significantly better than the salt spray resistance of coatings prepared with compositions of the art. ARDROX ^® AV 35D or SOCOPAC ^® 65H, as is clear from Table III below.

Table III: Salt spray resistance according to ASTM B-117 / ISO 9227: 2012 coatings prepared from compositions according to the invention or according to the prior art, applied to 2024-T3 aluminum alloy plates after degreasing, sodium attack and deoxidation, then dried for 7 days at room temperature. SB = solvent composition; WB = aqueous composition. DMA analyzes were performed indicating that the composition (1) according to the invention dries to form a "manipulable" free film having a non-zero level of crosslinking (identified by the presence of a rubber plateau succeeding the Tg transition). tan measured between 51 ° C and 55 ° C).

The cohesion of the films was then evaluated by a dry abrasion test according to the NF EN ISO 7784-2 standard. It turns out that the layer prepared with the composition according to the prior art: ARDROX ^® AV35D deteriorates from 20 cycles before being completely destroyed after 100 cycles.

The composition (1) according to the invention leads to a layer having a perfect resistance, namely 0.15% mass loss only after 500 cycles.

This test demonstrates that the composition (1) according to the invention which is a preferred composition comprising a modified urethane resin has a cohesion and cross-linking at its core capable of withstanding mechanical stresses.

Thus, the compositions according to the invention which advantageously contain modified alkyd resins lead to a drastic reduction of the drying time under degraded conditions, for example in a solvent-rich confined atmosphere, a better mechanical strength and anti-aging properties. corrosion superior to the compositions of the prior art, such as ARDROX ^® AV35D.

There is no limitation as to the choice of compound comprising at least one thiol function and / or at least one thione function. There are a large number of these compounds, of various structures that can be used in the compositions according to the invention and which give excellent results.

Thus, the organic corrosion inhibiting agent may be chosen from 2-Mercaptobenzothiazole or 2-MBT, also called Benzothiazole-2-thiol or 2 (3H) -Benzothiazolethione, 6-Methyl-2-mercaptobenzothiazole, the

Naphthal [1,2-d] thiazol-2 (1H) -thione, 7-methyl-benzothiazole-2-thiol, 4-methyl-2 (3H) -benzothiazolethione, 6-ethyl-2-benzothiazolinethione, 2,5-Dimercapto-1,3,4-thiadiazole or DMTD, mercaptobenzimidazole, and salts thereof, for example the metal or amine salts thereof. In particular, the organic corrosion inhibiting agent may be chosen from the sodium salt (1/1) of benzothiazolethione, the zinc salt (2: 1) of benzothiazolethione, and the cyclohexylamine salt of 2-mercaptobenzothiazole.

The preferred organic corrosion inhibiting agent that provides the best results in terms of anti-corrosion properties is 2-MBT or a salt thereof.

The composition according to the invention may further comprise at least one accelerator.

Advantageously, the composition according to the invention comprises from 2 to 20% by weight, preferably from 5 to 10% by weight of accelerator relative to the total weight of the composition.

In other words, the organic corrosion inhibiting agent chosen from mercaptans may be coupled, associated with one or more accelerators, for example with one or more vulcanization accelerators.

Here again, the combinations of mercaptans and accelerators can be very numerous and varied.

The accelerator may be in particular a thiocarbamate (thiocarbamates are vulcanization accelerators) such as 1-pyrrolidine-dithiocarbamate or PYRR.

The combination of a mercaptan with an accelerator leads to a synergy that can improve the excellent results in terms of corrosion resistance obtained with mercaptans alone.

The inorganic corrosion inhibitor can be chosen from corrosion inhibitors in the form of pigments, that is to say pigments that have a corrosion inhibiting action or corrosion inhibiting pigments.

Preferably, the inorganic corrosion inhibiting agent is chosen from metal oxides such as oxides of zinc, cerium IV, titanium, zirconium, iron, praseodymium (III) and antimony; metalloid oxides; zinc orthophosphosilicate calcium strontium aluminum hydrated or commercially HEUCOPHOS ZCP ^® ; synthetic amorphous silica exchanged with calcium ions; hydrated aluminum strontium polyphosphate; barium sulfate; zinc 5-nitroisophthalate; calcium and strontium phosphosilicate made organophilic; zinc phosphate especially rendered organophilic; zinc molybdate especially rendered organophilic; modified aluminum polyphosphate; strontium titanate; antimony tin oxide (ATO); molybdenum.

Examples of corrosion inhibitors in the form of pigments are given in Table IV below.

Table IV.

Advantageously, the inorganic corrosion inhibiting agent has a nanometric particle size.

By nanometric particle size, it is meant that the average size, for example the mean diameter (dso), of the nanometric particles is from 1 to 100 nm, preferably from 5 to 50 nm, more preferably from 10 to 50 nm, better from 10 to 20 nm. Particle size is measured by TEM (Transmission Electron Microscopy).

It has been found that the inclusion in the compositions according to the invention of an inorganic corrosion inhibiting agent having a nanometric particle size greatly improves the corrosion resistance of the coatings prepared from the compositions according to the invention. invention, for example on 2024-T3 aluminum plates compared to compositions containing corrosion inhibitors of non-nanometric size, for example micrometric.

Thus, for the same inhibitor, for example zinc oxide, introduced in the same proportions, generally between 1% and 5%, the coating containing the nanometric ZnO (average size (dso) of the particles of 10 to 20 nm) allows to resist between 1000 and 1400 hours exposure to salt spray (BS) with a dry layer thickness of 6 μιη, while that containing non-nanometric zinc oxide has a resistance of between 850 and 1000 hours under the same conditions.

Including a corrosion inhibitor in nanometric form therefore significantly improves the corrosion resistance performance of the coating.

It seems that there is an effect specific to the very nature of nanoparticles.

This effect would consist in filling the defects, cavities, cracks appearing during the aging and oxidation process at the level of the substrate and of its passivating layer (for example alumina) or even at the level of the coating itself.

In addition, to obtain high performance, a low content, for example from 2% to 10% by weight is sufficient.

The solvent may be selected from water, organic solvents and mixtures thereof; preferably the solvent comprises a majority by weight of water (more than 50% by weight); more preferably the solvent is water.

In other words, the composition according to the invention has the advantage of being formulated in a solvent medium, but also in an aqueous medium. The formulation in an aqueous medium has many benefits, for example: reduction of "VOCs", a composition which is less harmful to humans (that is to say operators responsible for applying the composition) ) and its environment, less odor problem and feeling of suffocation for example in the confined areas of the aircraft.

In other words, the composition (and method) according to the invention is advantageously environmentally friendly and meets the latest guidelines for environmental protection, directives because it preferably has a very low content. in organic solvents, generally less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight.

This is a difference and a further advantage of the composition (and the method according to the invention) compared to the processes of the prior art which implement higher levels of organic solvents.

This is the reason why, as we have seen above, the modified alkyd resins and in particular the urethane modified alkyd resins in an aqueous medium will be preferred, especially as these resins in an aqueous medium give the best properties in terms of terms of drying time and corrosion resistance.

The composition according to the invention may be in the form of an emulsion (water in oil or oil-in-water presence) or a solution.

The composition according to the invention may comprise, in addition, at least one dispersing agent.

The dispersing agent may be present in a proportion of 0.5% to 3% by weight of the total weight of the composition.

The dispersing agent may be the product known under the name DISPERBYK ^® 2010. The composition of the invention may further comprise at least one antifoaming agent.

The anti-foaming agent may be present in a proportion of 0.1% to 1% by weight of the total weight of the composition.

The anti-foaming agent can be for example the product known under the name of BYK ^® 1798. The composition according to the invention may comprise, in addition, at least one fungicidal agent.

The fungicidal agent may be present in a proportion of 0.01% to 0.5% by weight of the total weight of the composition.

The fungicidal agent may be, for example, sodium pyrithione.

The composition according to the invention may comprise, in addition, at least one bactericidal agent.

The bactericidal agent may be present in a proportion of from 0.01% to 0.5% by weight of the total weight of the composition.

The bactericidal agent can be chosen for example from

2-Benzoisothiazole-3 (2H) -one, 2-methyl-2H-isothiazol-3-one, and mixtures thereof.

The composition according to the invention may comprise, in addition, at least one dye and / or at least one pigment.

Each dye or pigment may be present at from 0.1% to 1% by weight of the total weight of the composition.

The pigments also include nacres, lacquers and mixtures thereof.

The pigments or dyes may be chosen from decorative pigments, in particular colored pigments or from UV pigments.

As mentioned above, some pigments may also act as corrosion inhibitors.

The composition according to the invention may comprise, in addition, at least one wetting agent.

The wetting agent may be present at from 0.1% to 5% by weight of the total weight of the composition.

By wetting agent, a surfactant is expected which lowers the surface tension of the composition according to the invention, rather than the interfacial tension between the composition and the surface of the substrate. The wetting agent improves the mixing of the various constituents of the composition and the adhesion of the anti-corrosion layer to a metal surface or other smooth surface. The wetting agent improves the wetting and spreading properties on various substrates, but also the quality of the formed network and the intrinsic anti-corrosion properties of the layer.

The composition according to the invention may further comprise at least one rheological agent.

The rheological agent may be present in an amount of 0.01% to 5% by weight, preferably 0.01% to 0.5% by weight, of the total weight of the composition.

The rheological agent may be chosen from polyurethane thickeners such as nonionic polyurethane ^® under the name TAFIGEL ^® PUR 60 and others.

The composition according to the invention may further comprise one or more additives chosen for example from anti-skin agents, drying agents, waxes, etc.

The additive or each of the additives may be present in a proportion of from 0.1% to 1.0% by weight of the total weight of the composition.

The composition according to the invention may comprise, in addition, at least one filler. The filler may be present in a proportion of 5% to 20% by weight of the total weight of the composition.

The filler may be chosen from micas, silicas, talcs, clays, and PTFE powders, which, because of their lamellar or nodular structure and / or their size, for example micrometric or nanometric, may optimize certain properties such as anti-sag properties, hardness, scratch resistance, and even the anti-corrosion properties of the layer.

The filler such as talc, mica, silica or clay is generally in the form of particles, or nanoparticles whose surface can be modified.

The composition according to the invention can be prepared by weighing and dispersing, mixing these components by means of any suitable mixing device.

For example, one can start by weighing the resin, the optional dispersing agent, and the anti-foaming agent and dispersing them, mixing, in a dispersion apparatus, mixing, adequate; then adding in order the organic corrosion inhibiting agent and the solid inorganic corrosion inhibiting agent in the dispersing apparatus and mixing them; then add in order the fungicide, the bactericide, the pigment and / or the dye in the dispersion apparatus and mix them; then pre-mix the wetting agent and the rheological agent, add them to the dispersion apparatus and mix them.

The invention also relates to a method for preparing an anti-corrosion layer on a surface of a substrate in which:

the composition as described above is deposited on the surface of the substrate to give a layer of the composition on the surface of the substrate;

said layer of the composition is dried, whereby the anti-corrosion layer is obtained on the surface of the substrate.

The method according to the invention has all the advantages related to the implementation in this process of the specific composition according to the invention.

In particular, the method according to the invention allows the preparation in a single pass, a single operation, a single step anti-corrosion layers having excellent anti-corrosion properties.

In other words, the process according to the invention makes it possible to prepare layers, films, with a dry thickness ranging from 5 to 50 μιη in a single pass, step, instead of several steps in the known analogous processes of product deposits. protection against corrosion. The film layers obtained are therefore, even for large thicknesses of homogeneous monolayer films and not films made up of several layers as with the methods of the prior art.

The thick layers obtained are excellent qualities, regular and without sagging, unlike the layers obtained with the methods of the prior art which implement a composition that is not that according to the invention.

The application method according to the invention is reliable, fast and of a lower cost than the methods of the prior art.

This process for preparing a layer, a corrosion protection film according to the invention, can easily be integrated into an existing conventional chain comprising other substrate treatments prior to or subsequent to the deposition of said film.

The substrate according to the invention may be of any material capable of receiving a anti-corrosion layer. The process according to the invention can be implemented with a wide variety of materials, always with excellent results in terms of properties and, above all, anti-corrosion properties of the layer obtained.

The substrate may be a material selected from metals; metal alloys; organic or mineral glasses; organic polymers such as thermoplastic polymers (plastics); wood ; ceramics; textiles; concretes; the papers ; stone ; carbon fibers; and composite materials comprising many of the previously enumerated materials, such as composite materials comprising carbon fibers such as carbon fiber reinforced plastics; this material possibly being plated and / or having undergone a surface treatment and / or being coated, for example painted.

Advantageously, the substrate may be made of a material chosen from aluminum; titanium; the copper ; the iron ; magnesium; and alloys thereof, such as steels, for example, stainless steels, aluminum alloys, such as 2024-T3 aluminum alloy, and Inconel; the surface of the substrate having optionally been plated and / or having undergone a surface treatment and / or being coated, for example painted.

Aluminum alloys include 7075, 6056 and 2024 alloys such as 2024-T3 aluminum alloy.

Titanium alloys include Ti6-4, Ti-15-3-3-3, Ti-6-2-2-2-2 and Ti-3-2-5 alloys.

The substrate may be of any shape but is generally in the form of a plate, sheet or sheet. The method according to the invention, however, allows the deposition of layers on surfaces of very complex geometry.

The substrate may consist in particular of several plates composed of different materials, riveted. The protection against corrosion imparted by the anti-corrosion layer according to the invention is effective both on the surface of the substrate (s) but also inside the rivets.

The surface on which the layer is deposited may be only a part of the total surface of the substrate, but it may also be all of said surface, for example can with the method according to the invention deposit a layer on both sides of a sheet substrate.

Prior to the deposition of the composition, the surface is preferably cleaned and / or activated and / or pickled by chemical and / or physical and / or mechanical treatment.

Indeed, this cleaning is important in order to obtain good adhesion of the deposited layer. These cleaning processes are known to those skilled in the art: it may be a wet cleaning, for example by acidic or basic solutions, an alkaline or solvent degreasing or a cleaning by lane. dry, for example by shot blasting and / or sanding and / or flaming, etc.

For some carriers, a particular treatment, such as adhesion promoter, may be added.

Such cleaning and / or activation treatments are known to those skilled in the art and are widely described in the prior art.

On the surface of the substrate, preferably cleaned and activated, depositing the anti-corrosion composition according to the invention as described above.

The compositions according to the invention allow the deposition of thin layers or films, but also the deposition of thicker layers or films.

Advantageously in a single operation, a layer of the composition is deposited with a wet thickness of 10 to 100 μιη, preferably 40 to 50 μιη.

Advantageously, the anti-corrosion layer (that is to say the final dried layer) has a thickness in the dry state of 5 to 45 μιη, preferably 10 to 25 μιη, more preferably 20 to 25 μιη. .

The thickness of the anti-corrosion layer (that is to say of the dried final layer) is a function of the dry extract of the composition.

The composition can be deposited by any known technique, for example the composition can be deposited by a technique selected from spraying for example by means of a gun, spraying, soaking, brushing, or aerosol deposition.

In order to finish or reach areas difficult to access by the techniques already mentioned, an aerosol deposit is possible. Preferably, the composition is applied by spraying, for example by means of a spray gun, in a very simple manner, similar to the application of a paint or varnish.

The desired dry thickness of the layer can be easily obtained by, for example, changing the settings of the guns, the type of gun and the distance of application.

The deposition operation, application, of the composition according to the invention on the surface is generally carried out at a temperature of 7 ° C to 40 ° C, preferably 15 ° C to 25 ° C, for example 23 ° C .

At the end of the deposition, a substrate is obtained, the surface of which is coated with a layer of the composition according to the invention. This layer is a layer that can be described as a "wet" layer because it still contains solvent such as water.

Generally, the drying of the composition layer is carried out at room temperature, and in the open air, for a period of 15 minutes to 7 days, preferably for a period of 15 to 60 minutes.

Indeed, a drying time 15 to 60 min is sufficient to allow handling or so that the layer is recoverable, while a longer time, preferably 7 days is necessary to obtain a total crosslinking.

By ambient temperature is generally meant a temperature of 15 ° C to 30 ° C, especially 20 ° C to 25 ° C.

It is preferable to deposit only a single anti-corrosion layer by the process according to the invention thus forming a monolayer coating, this anticorrosion layer generally having a dry thickness as defined above.

According to the invention, excellent properties are indeed obtained with such a single layer, such a monolayer coating.

It is also possible to deposit, but this is generally not preferred, several anti-corrosion layers thus forming a multilayer coating. Generally 1 to 3 layers, preferably 1 layer, can be deposited.

Depending on the various additives incorporated in the composition, the anti-corrosion layer may have various properties.

Advantageously, said surface is coated only with said anti-corrosion layer, preferably containing a dye and / or a pigment, thus forming a monolayer coating on said surface.

In this case, preferably, the substrate is a metal or a metal alloy and said monolayer coating is a coating called "Direct to Metal" or "DTM".

The invention also relates to an anti-corrosion layer that can be prepared by the method described above.

The invention further relates to a substrate comprising at least one surface coated with at least one anti-corrosion layer as described above.

Advantageously, said surface is coated only with said anticorrosion layer (no other coating layer being present), and preferably said layer contains at least one dye and / or a pigment.

In other words, preferably, the anti-corrosion layer may be applied in the form of a monolayer coating, colored or not, pigmented or otherwise, on the surface of the substrate.

In other words, such a single anti-corrosion layer can be used alone as a protective anti-corrosion coating.

Such a single anti-corrosion layer thus forms a monolayer coating on said surface; preferably the substrate is a metal or a metal alloy and said monolayer coating is then a coating called "Direct to Metal" or "DTM".

The substrate may consist of part or all of an aircraft such as an airplane, a seaplane, a helicopter, or a drone; a spacecraft; a rocket; a ship; a hovercraft; an offshore platform; a motor vehicle such as a car, a motorcycle, or a truck; a gas pipeline, an oil pipeline, or an aqueduct; a railway vehicle such as a locomotive or a wagon; a wind turbine; of a tidal turbine.

The invention also relates to the use of the anti-corrosion layer according to the invention as described above for imparting corrosion resistance properties to a surface of a substrate, in particular to a surface made of a material selected from metals such as aluminum, metal alloys such as aluminum alloys, and composite materials comprising a metal or metal alloy.

Preferably, the substrate is aluminum or aluminum alloy, and the layer anti-corrosion gives the surface a corrosion resistance in the salt spray corrosion resistance test, in accordance with the NF EN ISO 9227: 2012 standard, of more than 1000 hours, preferably more than 2000 hours, and more preferably more than 3000 hours for a layer with a thickness of 25 μιη in the dry state

Advantageously, said surface is coated only by said anti-corrosion layer

(dried); in other words, said anti-corrosion layer is used alone, as a single layer on the surface.

In other words, said single anti-corrosion layer forms a monolayer coating on the surface.

When this surface is a metal or metal alloy surface, such a monolayer coating is called a "Direct To Metal" ("DTM") coating.

This anti-corrosion "DTM" coating gives very good properties of corrosion resistance and mechanical protection to the substrate.

The reason for this is that the anti-corrosion layer according to the invention, or prepared by the process according to the invention, allows, surprisingly alone, by itself - without another layer, such as a layer The primer or coat of paint may be used to simultaneously impart corrosion resistance, chemical protection, mechanical strength, scratch protection, a metal or metal alloy surface.

This avoids the deposition of other layers in addition to the anti-corrosion layer and leads to the reduction of cycle times and production, and the lightening of the structure, which are particularly interesting, for example for the reduction costs in the aerospace industry.

Finally, the method according to the invention is simple, reliable, fast and less expensive than the processes of the prior art because a single coating step and a single layer can replace several. DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS

EXAMPLES.

In the following experimental examples, compositions, formulations according to the invention are prepared.

Then, these compositions, formulations according to the invention are deposited, applied in the form of films on the surface of substrates, namely the surface of aluminum alloy plates.

The substrates coated with the films are dried and the properties of the films according to the invention thus prepared are evaluated.

Example 1

• Preparation of a composition, formulation, according to the invention.

We weigh:

79.74 g of an emulsion in water modified polyurethane alkyd resin (PU) available under the tradename WorléeSol ^® E 150 W from the company Worlée Lauenburg, Germany;

2.00 g of a dispersing agent which is a copolymer comprising groups having affinity for pigments, available from BYK under the name DISPERBYK ^® 2010; and

- 0.30 g of a defoamer available from BYK under the name (BYK ^® 1798).

The three components thus weighed are placed together in a disperser and the mixture is stirred for 5 minutes.

Then, in order, in the vortex of agitation formed in the disperser:

8.5 g of an organic anti-corrosion pigment, 2-MBT, available from the company LANXESS under the trade name VULKACIT MERCAPTO / C; and 8.5 g of an inorganic anti-corrosion pigment, Zinc Calcium Strontium Aluminum Silicate Hydrate orthophosphate, available from HEUBACH company under the trade name HEUCOPHOS ^® ZCP +. The mixture is maintained for 10 minutes with vigorous stirring, namely at a speed of 1000 rpm.

Then add in order:

0.072 g of a fungicide, Sodium Pyrithione;

0.012 g of a bactericide, 2-Benzisothiazole-3 (2H) -one, 2-methyl-2H-isothiazol-3-one;

0.10 g of an anti-UV pigment, in the form of a solution of sulfostryryl biphenyl sodium salt; and

0.40 g of a pigment, the yellow color 11680 46%. The mixture is kept at least 30 minutes with stirring.

A premix of 0.30 g of a wetting agent, dipropylene glycol methyl ether (DPGME) and 0.073 g of a rheological agent which is a nonionic polyurethane available from Munzig ^{® are} prepared separately.

This premix is then added to the vortex and stirring is continued for 30 minutes.

• Substrates.

The substrates are panels, plates, 2024-T3 aluminum alloy. · Preparation of substrates

The copper present in the 2024-T3 aluminum alloy tends to deteriorate the naturally occurring oxide protective layer. Therefore, it is important to prepare the surface of said alloy to remove surface contaminants, oxides that could interfere with subsequent steps of the film preparation process, and the plates thus undergo four successive surface treatments. In a first surface treatment, the plates, panels, of aluminum alloy (2024-T3) are first degreased with DIESTONE ^® DLS in order to eliminate dust and other contaminants on the surface of the plates.

Then, during a second surface treatment, the plates are degreased in a SOCOCLEAN ^® A3431 bath whose volume concentration is 10%, heated between 40 ° C and 45 ° C, and with gentle stirring, for 5 to 30 minutes. minutes. The plates are then rinsed twice. The first rinsing is done with city water for two minutes and the second rinsing is carried out with distilled water for 2 minutes also.

The third surface treatment is a sodium attack in a soda bath whose concentration is 40 g / l, heated between 50 ° C and 65 ° C for 1 to 5 minutes (s). The plates are then rinsed twice with distilled water for 2 minutes.

The fourth surface treatment is a deoxidation treatment in a nitric acid bath whose concentration is between 400 and 500 g / l. The plates are immersed in this bath at room temperature for 5 to 15 minutes.

The plates are then rinsed twice with distilled water for 2 minutes and then dried for a few minutes at 60 ° C.

• Plates must be used within 12 hours after these surface treatments. · Application of the formulation on aluminum alloy substrates.

The formulation is applied, deposited by spraying with a KREMLIN ^® brand gun onto the aluminum alloy plates, in order to obtain a film, a layer having a wet thickness of 60 μιη.

The plates thus coated with a film or wet layer are then left at ambient temperature for 7 days, after which aluminum alloy plates coated with a protective layer against corrosion are obtained, in the state dry.

The samples, i.e., said aluminum alloy plates coated with a protective layer against corrosion, in the dry state are then ready to be characterized. • Characterization of the samples.

Thickness :

The average thickness of the deposited film or layer, in the dry state, is measured according to the ISO 2360: 2003 standard with a MiniTest 7400 type device marketed by ElektroPhysik equipped with the N4 probe for panels, alloy plates Aluminum (Measurements based on eddy currents).

10 measurements are made on the surface of the sample. The average thickness is raised.

This thickness is 20-25 μιη.

Resistance to salt spray corrosion ("Sait Spray Test" or "557 ^" ):

The salt spray corrosion resistance test is used to estimate the corrosion resistance of metallic materials. This test is performed according to the ISO 9227: 2012 standard. The coated aluminum alloy plates are placed in an enclosure (Q-FOG Cyclic Corrosion Tester Q-Panel) at 35 ° C ± 2 ° C on supports with an angle of 20 ° ± 5 ° to the vertical . The plates are exposed to an artificial mist from a solution of sodium chloride. This solution contains 50 g / L ± 5 g / L of sodium chloride, and its pH is between 6.5 and 7.2 at 25 ° C ± 5 ° C. The plates are observed regularly and the presence of corrosion (uniform corrosion, pitting, etc.) is noted.

Corrosion is less than 3% of the surface after 3000 hours for a dry film thickness of 25 μιη.

Claims

1. Anti-corrosion composition, characterized in that it comprises:

a) at least one organic binder resin;

c) optionally a solvent; and

d) at least one solid inorganic corrosion inhibiting agent.

2. Composition according to claim 1, comprising in% by weight relative to the total weight of the composition:

from 30% to 60% by weight of the organic binder resin;

from 5% to 20% by weight of the solid inorganic corrosion inhibiting agent;

from 0% to 50%, preferably from 10% to 40%, by weight of the solvent.

3. Composition according to any one of the preceding claims, in which the binder resin is chosen from alkyd resins, modified alkyd resins such as urethane-modified alkyd resins or epoxy-modified alkyd resins, terpene resins, acrylic resins, and the like. styrene-acrylic resins, hydrocarbon resins, and vinyl resins such as vinylic acrylic resins and vinyl styrenic resins.

4. Composition according to any one of the preceding claims, wherein the binder resin is chosen from urethane modified alkyd resins also called alkyd urethane resins.

The composition according to any one of the preceding claims, wherein the organic corrosion inhibiting agent is selected from the group consisting of 2-Mercaptobenzothiazole or 2-MBT, also called Benzothiazole-2-thiol or 2 (3H) -Benzothiazolethione, 6-Methyl-2-mercaptobenzothiazole, the

Naphthal [1,2-d] thiazol-2 (1H) -thione, 7-methyl-benzothiazole-2-thiol, 4-methyl-2 (3H) -benzothiazolethione, 6-ethyl-2-benzothiazolinethione, 2,5-Dimercapto-1,3,4-thiadiazole or DMTD, mercaptobenzimidazole, and salts thereof, for example the metal or amine salts thereof.

The composition according to claim 5, wherein the organic corrosion inhibiting agent is selected from the sodium salt (1/1) of Benzothiazolethione, the zinc salt (2: 1) of Benzothiazolethione, and the salt of cyclohexylamine of 2-mercaptobenzothiazole.

A composition according to any one of the preceding claims, which further comprises at least one accelerator, such as a thiocarbamate such as 1-pyrrolidine-dithiocarbamate or PYRR.

8. Composition according to claim 7, comprising from 2 to 20%, preferably from 5 to 10% by weight of accelerator relative to the total weight of the composition.

9. Composition according to any one of the preceding claims, in which the inorganic corrosion inhibitor is chosen from corrosion inhibitors in the form of pigments.

10. Composition according to any one of the preceding claims, in which the inorganic corrosion inhibiting agent is chosen from metal oxides such as oxides of zinc, cerium (IV), titanium, iron zirconium, praseodymium (III) and antimony; metalloid oxides; zinc orthophosphosilicate calcium strontium aluminum hydrate; synthetic amorphous silica exchanged with calcium ions; hydrated aluminum strontium polyphosphate; barium sulfate; zinc 5-nitroisophthalate; the phosphosilicate of calcium and strontium rendered organophilic; zinc phosphate especially rendered organophilic; zinc molybdate especially rendered organophilic; modified aluminum polyphosphate; strontium titanate; antimony tin oxide (ATO); and molybdenum.

A composition according to any one of the preceding claims, wherein the inorganic corrosion inhibiting agent has a nanoscale particle size.

12. Composition according to any one of the preceding claims, in which the solvent is chosen from water, organic solvents and their mixtures; preferably the solvent comprises a majority by weight of water; more preferably the solvent is water.

13. Composition according to any one of the preceding claims, which further comprises at least one dispersing agent, preferably in a proportion of 0.5% to 3% by weight of the total weight of the composition.

A composition according to any one of the preceding claims, which further comprises at least one anti-foaming agent, preferably in an amount of from 0.1% to 1% by weight of the total weight of the composition.

15. A composition according to any one of the preceding claims, which further comprises at least one fungicidal agent, preferably in a proportion of 0.01% to 0.5% by weight of the total weight of the composition.

16. A composition according to any one of the preceding claims, which further comprises at least one bactericidal agent, preferably in a proportion of 0.01% to 0.5% by weight of the total weight of the composition.

A composition according to any one of the preceding claims which further comprises at least one dye and / or at least one pigment, preferably from 0.1% to 1% by weight of the total weight of the composition for each dye or pigment.

18. Composition according to any one of the preceding claims, which further comprises at least one wetting agent, preferably in a proportion of 0.1% to 5% by weight of the total weight of the composition.

19. A composition according to any one of the preceding claims, which further comprises at least one rheological agent, preferably in a proportion of 0.01% to 5% by weight, more preferably in a proportion of 0.01% to 0, 5% by weight, of the total weight of the composition.

20. Composition according to any one of the preceding claims, which further comprises one or more additive (s), chosen (s) for example from anti-skin agents, drying agents, waxes, preferably each at a rate of 0.1. % to 1% by weight of the total weight of the composition.

21. The composition of any one of the preceding claims, which further comprises at least one filler, preferably from 5% to 20% by weight of the total weight of the composition.

22. A method for preparing an anti-corrosion layer on a surface of a substrate in which:

the composition according to any one of claims 1 to 21 is deposited on the surface of the substrate to give a layer of the composition on the surface of the substrate;

23. The method of claim 22, wherein, in a single operation, a layer of the composition is deposited with a wet thickness of 10 to 100 μιη, preferably 40 to 50 μιη.

24. The method of claim 22 or 23, wherein the anti-corrosion layer has a thickness in the dry state of 5 to 45 μιη, preferably 10 to 25 μιη, more preferably 20 to 25 μιη.

25. A method according to any one of claims 22 to 24, wherein the composition is deposited by a technique selected from spraying for example by means of a gun, spraying, soaking, brushing, or depositing by aerosol.

The method of any one of claims 22 to 25, wherein the substrate is of a material selected from metals; metal alloys; organic or mineral glasses; organic polymers such as thermoplastic polymers; wood ; ceramics; textiles; concretes; the papers ; stone ; carbon fibers; and composite materials comprising many of the previously enumerated materials such as composite materials comprising carbon fibers such as carbon fiber reinforced plastics materials; this material possibly being plated and / or having undergone a surface treatment and / or being coated, for example painted.

27. The method of claim 26, wherein the substrate is of a material selected from aluminum; titanium; the copper ; the iron ; magnesium; and alloys thereof, such as steels, for example stainless steels, aluminum alloys, such as 2024-T3 aluminum alloy, and Inconel; the surface of the substrate having optionally been plated and / or having undergone a surface treatment and / or being coated, for example painted.

28. A method according to any one of claims 22 to 27, wherein prior to the deposition of the composition, the surface is cleaned and / or activated and / or pickled by a chemical treatment and / or physical and / or mechanical.

29. A method according to any one of claims 22 to 28, wherein the drying of the composition layer is carried out at room temperature, and in the open air, for a period of 15 minutes to 7 days, preferably during a duration of 15 to 60 minutes.

The method of any one of claims 22 to 29, wherein said surface is coated only with said anti-corrosion layer, preferably containing a dye and / or a pigment, thereby forming a monolayer coating on said surface, preferably the substrate is a metal or a metal alloy and said monolayer coating is a coating called "Direct to Metal" or "DTM".

Anti-corrosion layer capable of being prepared by the method according to any one of claims 22 to 30.

32. Substrate comprising at least one surface coated with at least one anti-corrosion layer according to claim 31.

33. The substrate according to claim 32, at least one surface of which is coated solely with said anti-corrosion layer, preferably containing a dye and / or a pigment, thus forming a monolayer coating on said surface, preferably the substrate is in one. metal or a metal alloy and said monolayer coating is a coating called "Direct to Metal" or "DTM".

34. Substrate according to claim 32 or 33 which is constituted by a part or the whole of an aircraft such as an airplane, a seaplane, a helicopter, or a drone; a spacecraft; a rocket; a ship; a hovercraft; an offshore platform; a motor vehicle such as a car, a motorcycle, or a truck; a gas pipeline, an oil pipeline, or an aqueduct; a railway vehicle such as a locomotive or a wagon; a wind turbine; of a tidal turbine.

35. Use of the anti-corrosion layer according to claim 31, for imparting corrosion resistance properties to a surface of a substrate, in particular to a surface made of a material chosen from metals such as aluminum and alloys. metals such as aluminum alloys, and composite materials comprising a metal or a metal alloy.

The use of claim 35, wherein the substrate is aluminum or an aluminum alloy, and the anti-corrosion layer imparts corrosion resistance to the surface in the salt spray corrosion test, according to standard NF EN ISO 9227: 2012, more than 1000 hours, preferably more than 2000 hours, and more preferably more than 3000 hours for a layer with a thickness of 25 μιη in the dry state.

37. The use of claim 36, wherein said surface is coated only by said anti-corrosion layer.